Fluorinated compound and method of producing same



' March 6, 1945. P. J. GAYLOR 2,370,787

FLUORINATED COMPOUND AND MTHOD OF PRODUCING SAME Original Filed Jan. l1, 1934 51 H22, Vml 'H2O I' ZY,

lll c O y Le runen/05 rinated products.

Patented Mar. 6, 1945 FLUORINATED COMPOUD AND METHOD 0F PRQDUCING SAME Peter J. Gaylor, Union, N. J., assignor to Standard Oil Development Company, a corporation of Delaware Original application January 11, 1934, Serial No.

706,230, now Patent No. 2,186,916, dated J anuary 9, 1940. Divided and this application February 2, 1939, Serial No. 254,209

4 Claims.

This invention deals with the preparation and use of relatively high boiling oils and solids containing iiuorine. It especiallyinvolves the pro- I duction of fluoro derivatives boiling above 200 C.

The present application is a division of my copending application Ser. No. 706,230 filed under my former name of Peter J. Wiezevich on January 11, 1934, now U. S. Patent 2,186,916-issued January 9, 1940. f'

In the drawing is shown'in diagrammatic form an' apparatus-for producing fluorine-containing chlorine compounds are too unstable, especially in the presence of moisture andmetals, giving off hydrochloric acid very readily,u and often polymerizing to dark ,colored heavy products. The pure aromatic chloro derivatives, such .as chlorinated diphenyls or naphthalenes, have been found to be'quite stable at ordinary temperatures, but one of the main objections of such compounds is the fact that the chlorine affects the boiling point too markedly, so that if, for example, a really non-inflammable material is desired, the amount of chlorine required to give this effect would produce only solid products having very limited uses.

Fluorine compounds are much more stable than the corresponding chlorine derivatives, making it possible to utilize aliphatic compounds for purposes hitherto considered impractical with chlo- Furthermore, in the case of aromatic hydrocarbons, for a given boiling point of the product, it is possible to introduce a considerably higher percentage of fluorine than chlorine, givinga much wider range of liquid and solid non-inflammable compounds for selection. Other advantages will be apparent from the subsequent description.

As raw materials for this processy I employ organic substances, generally those capable of giving fluoro derivatives boiling above 400 F. and preferably those organic compounds boiling above 400 F. Such compounds as petroleum distillates, as for example kerosene, gasoil, lubricating oil, fuel oil, or cracking coal tar fractions, extracts of petroleum or its fractions obtained with solvents such as SO2, phenol, nitrobenzene, furfural, cresol and other similar agents, treated oils, as white or refined oils, propane treated oils, hydrogenated or hydroiined oils. products o\l carbonization of mineral oils, coal, llgnite, and the like, animal, vegetable, and fish oils and other glycerides, high boiling esters such as dibutyl phthalate, tricresyl phosphate, chlorinated esters, and other esters as those described in my co-pendlng application No. 690,234 led on September 20, 1933. now U. S. Patent 2,104,408 issued January 4, 1938. Other compounds which may be so treated are chlorinated petroleum products, oxidation products of oils and waxes, sulfur. containing compounds, high boiling alcohols, acids, ketones, amines, amides, aldehydes, ethers, heterocyclic compounds such as pyridine, thlophene, etc., aromatic compoundsA or coal tar products as naphthalene, diphenyl, benzene, toluene, xylene, di-

phenyl oxide, diphenylene oxide, and the like, chlorinated compounds such as chlorinated or brominated wax, chlorinated naphthalene, di-

described in my co-pending application Serial No.

701,343, iiled on December 7, 1933, now U. S. Patent 2,123,641 issued July 12, 1938, as well as hydro rubber, rubber, chlorinated rubber, wax, petrolatum, thickened glycerides or voltolized mineral or glyceride oils, or stabilized esters such as those mentioned in co-pending application No. 690,235 iiled on September 20, 1933, inthe names of Peter J. Wiezevich and Luther B. Turner, now U. S.

ist4

Patent 2,107,316 issued February 8, 1938, aromatic materials similar to those described in my co-pending applicationJSerial No. 685,493 tiled on August 16, 1933. now U. S. Patent 2,079,783 issued May 11, 1937, celluloseesters and ethers, resins such as the Bakelite, cumarone, and other types, rosln, shellac, plastics, products obtained shown in the drawing. Numeral I is a generator l for the production or hydrogen iluoride, equipped with stirrer 2 and suitable means of heating. These may be constructed oi copper, iron coated with lead, resistant plastic, or other suitable corrosion resistant material. Suliuric acid and calcium fluoride used for the production of the yhydrogen fluoride may be introduced into the generator at 3, and the sludge formed drawn oifat` I, while hydrogen iiuoride vapor is led out at directly to a scrubber 3, or through line 3l ior indirect-uorination o! chloro compounds as will be explained later. Scrubber 6l, constructed of resistant metal or plastic is equipped with baies or plates, 1, upon which may be circulated a puritying solution such as a solution oi iuming sul- Iuric acid containing 2l0% potassium dichroof apparatus, I3, the HF is caused to react with the KF to produce the double salt KFHF which is removed'at I0. Any unused l-IE may be recirculated by forcing it throughline I1.

The double salt KFHF (I `9) is then electrolyzed in a copper eiectrolyzer I8 equipped with carbon electrodes and suitable insulating caps 2l made of iiuorspar or the like, and heated by some suitable means. It is preferable to keep the temperature at 200350 C, in the electrclyzer,

so that by a current of 10-20 amperes at about 15 volts, a reasonably steady stream of iiuorine may be maintained at 22 and drawn o to storage through line 35, or led directly into fluorinator 28. Hydrogen will be liberated at 25, and may be collected in a suitable reservoir. The pressure on both sides ofthe V of the electrolyzer must be kept at the same value as closely as is practical, since otherwise the fiuorine or hydrogen would mix. Y

The iluorine so formed is led into uorinator 26 equipped with jacket; 30 and inner coil 21 capable of cooling or heating the contents 33, while they are `,tirred with stirrer 32. The material to be fluorinated, such as mineral or vegetable oil, naphthalene, diphenyloxide, etc. is led into the vessel through 29 and reacted with the iluorine dispersed through it by a spray forming arrangement 28.

A suitable solvent or liquid,y reaction medium such as carbon tetrachloride. or the like may be introduced with the raw material in order to decrease the violence of the reaction. An inert gas or vapor such as nitrogen, `carbon dioxide, and the like may also be introduced with the uorine (from l0 to 90% of the total mixture) through line 36 to assist inthe same manner. It is sometimes advantageous to introduce chlorine, hydrogen chloride, hydrogen iluoride or other halogen or halogen compounds with the uorine. Any

, HF formed in the reaction may be bled ofi at 3| and collected or introduced at some point such as 3l for recovery. In the case of very reactive compounds such as naphthalene and many other resistant properties, they serve as valuable comv.atmospheric pressure.

lower may be used.

400 F., unsaturated hydrocarbons, unsaturated j glyceridea drying oils, oxygenated compounds,

etc. is to lead the HF gas from 3l directly into the fluorinator 26 through line 35.. This is also a means of stabilizing unstable organic compounds. Heat may also be used, as for example temperatures of 40 F., 100 F., 200 F., 450 F. or even 500 F. with or without the use of super- In such cases it is generally desirable `to carry' out the reaction in presence of a iluorination catalyst such as iodine, and the like, or a metal halide or metal fluoride as for example antimony penta or tri-chloride, bismutlrtrichloride, boron triiiuoride, etc. For example, chlorinated castor oil or chlorinated wax may be introduced into the uorinator at 28, together with some aritimony chloride (say V2 to 20% by weight), and reacted with HF entering at 22. A solvent such as kerosene, naphtha, whiteoil, or cyclohexane may be added with the charge; After the reaction has progressed to the desired stage, the products may be drawn oi! at 31, or they may be drawn oir continuously while a continuous stream of raw material is fed in. In many cases it is not necessary to replace all of the chlorine in the material treated, and the resulting chloro-fluoro compound can be employed for a variety of purposes. Sometimes the products are suitable even when only very small quantities of fluorineare present. l

The materials produced according to this invention may be employed as blendingagents in lubricants, as for example as extreme pressure lubricants or fire resisting lubricants, and they may be used as such, without diluents, for the preparation of lubricating oils, turbine oils, greases, and the like. For example, a blend of 5to 50% or more of a nuoro compound in a mineral, synthetic or glyceride oil is satisfactory for reducing the inflammability, While 0.01 to 5% of the iluoro Y or nuoro-chloro compound may be used as an oxidation or polymerization inhibitor, or as a blending agent to improve the oil in other respects.

'I'he products, such as those containing between 5 to 60% rluorine or more, may also be employed as coatings, impregnating materials for ilbrous substances as wood, cloth, and the like, as ingradients in paints, varnshes, lacquers and enamels. Due to their stability and combustion pounding agents in rubber, asphalts, resins, nreproofing compounds, building materials, and the like, especially when they contain from 1 to 50% or even as high as '10% fluorine. They are valuable as blending agents in fuels, solvents,

' waxes, plastics, and other similar products, alone,

or together with dyes, pigments, llers and compounding agents. They also serve as extraction agents for improving the quality oi light and heavy petroleum hydrocarbons, as precipitating agents, and as non-igniting oils for lubrication, insulation, for use in transformers, cables, condensers, and other similar purposes, especially when they contain from approximately 10 to 60% fiuorine. Plastic compositions containing 5 or 10 to 60% of such fluorinated organic compounds Insuch acaso a slurry of solid naphthalene in carbon disulde may be ao 1. A liquid insulating composition comprising are very suitable as'moulding materials for various articles of furniture, equipment, etc. Resins may be fluorinated, especially when dissolved in solvents or admixed with other ingredients so as to contain 5 to 50% iluorine or even more. Various other materials such as paper, wood. cloth, leather, and the like may be'treated with iluorine to improve .the qualities thereof.

The nuoro compounds produced by the methods described may also be employed to advantage as raw materials for chemical syntheses. For example, they may be condensed with aromatic hydrocarbons, other aromatic compounds, halogenated compounds, and the like, to yield ex-v cellent blending agents for lubricants or fuels. They may also be reacted'with materials of the sodium polysuide type to yield useful plastics and oils. Numerous other condensation, polymerization, deiuorination. and addition reactions may be ,carried out 'to I claim:

a fluorinated derivative of mineral wax, said derivative containing approximately 10 to 60% iluorine by weight.

2. A liquid insulating composition comprising a fluorinated derivative of petrolatum, said de- ,rivative containing approximately 10 to 60% -derivative containing approximately 10 to 60% iiuorine by weight.

4. An insulating composition comprising a brous organic substance impregnated with a fluorinated derivative of petrolatum, said derivative` containing approximately 10 to 60% of produce useful products. 80

iiuorine by weight.

PETER J. GAYLOR. 

